The ability to control interfacial properties, such as wettability, is of great importance in emerging technologies as diverse as protein engineering, microfluidic devices, and antifouling water filtration systems. An extraordinary array of approaches that involve topological construction of micro- and nanostructures, surface modification with low-surface-energy molecules, utilization of stimuli-responsive materials have been developed to alter the wettability of a material. The vast majority of these approaches, however, rely on structures that are firmly coupled to supporting substrates and thus regarded as integrated systems. In contrast, the approach that leads to an easily scalable procedure to create appropriate large-scale free-standing structures for practical applications is a substantial challenge as assembly methods for simultaneous control of features at lengths from the nanometer scale to the macroscale remain elusive. Free-standing membrane structures, such as layer-by-layer assembled polymer films, carbon nanotube membranes and sheets, have been recently reported, but they have limitations for systems that need to require low-cost fabrication, high thermal stability, high levels of control over a wide range of wetting behavior, and high degrees of wetting reversibility.